WO2008021602A2 - Structures including catalytic materials disposed within porous zeolite materials, systems and methods for using the same, and methods of fabricating catalytic structures - Google Patents
Structures including catalytic materials disposed within porous zeolite materials, systems and methods for using the same, and methods of fabricating catalytic structures Download PDFInfo
- Publication number
- WO2008021602A2 WO2008021602A2 PCT/US2007/069005 US2007069005W WO2008021602A2 WO 2008021602 A2 WO2008021602 A2 WO 2008021602A2 US 2007069005 W US2007069005 W US 2007069005W WO 2008021602 A2 WO2008021602 A2 WO 2008021602A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalytic
- zeolite material
- pores
- zeolite
- angstroms
- Prior art date
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 196
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 190
- 239000000463 material Substances 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 73
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 98
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000011148 porous material Substances 0.000 claims abstract description 87
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 52
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 50
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 38
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 37
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 239000005751 Copper oxide Substances 0.000 claims abstract description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims description 24
- 150000004706 metal oxides Chemical class 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000007769 metal material Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011852 carbon nanoparticle Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000013528 metallic particle Substances 0.000 claims 19
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 15
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 9
- -1 for example Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006194 liquid suspension Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000008936 AlbP Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/22—Higher olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Definitions
- the present invention relates to catalytic materials, structures, systems, and methods. More particularly, the present invention relates to catalytic structures including zeolite materials, and to systems and methods for synthesizing hydrocarbon molecules from hydrogen and at least one of carbon monoxide and carbon dioxide using such catalytic structures. The present invention also relates to methods of fabricating catalytic structures that include zeolite materials.
- Carbon dioxide gas (CO 2 ) may be converted into liquid fuels such as, for example, hydrocarbon molecules of between about 5 and about 12 carbon atoms per molecule (e.g., gasoline) through multi-step reactions.
- carbon dioxide (CO 2 ) gas and hydrogen (H 2 ) may be converted to carbon monoxide (CO) gas and water (H 2 O) through the Reverse Water-Gas Shift Reaction, which is shown by Reaction [1] below.
- Synthesis gas which is a mixture of carbon monoxide gas (CO) and hydrogen gas (H 2 ) then may be produced from the reaction products of the Reverse Water-Gas Shift Reaction by adding additional hydrogen gas (H 2 ) to the reaction products.
- This synthesis gas may be further reacted through either Fischer-Tropsch (FT) processes, or through methanol synthesis (MS) plus methanol-to-gasoline (MTG) processes, to provide liquid fuels.
- FT Fischer-Tropsch
- MS methanol synthesis
- MMG methanol-to-gasoline
- Fischer-Tropsch processes include various catalyzed chemical reactions in which synthesis gas is converted into liquid hydrocarbons in a reactor in the presence of a catalyst and at temperatures between about 200 0 C and about 35O 0 C.
- Catalysts used in Fischer- Tropsch processes include, for example, iron, cobalt, nickel, and ruthenium. While various interrelated reactions may occur in Fischer-Tropsch processes, the overall reaction process may be generally represented by Reaction [2] below.
- synthesis gas may also be reacted by first performing a methanol synthesis (MS) process, and then performing a methanol-to-gasoline (MTG) process to produce liquid fuels.
- Methanol synthesis (MS) processes involve the catalytic conversion of carbon monoxide, carbon dioxide, hydrogen, and water to methanol and other reaction byproducts.
- the methanol synthesis reactions may be generally represented by Reactions [3], [4], and [5] below. [3] CO + 2H 2 ⁇ CH 3 OH
- the methanol-to-gas (MTG) process involves the conversion of methanol to hydrocarbon molecules using zeolite catalysts, which are described in further detail below.
- the methanol-to-gas (MTG) process occurs in two steps. First, methanol is heated to about 300 0 C and partially dehydrated over an alumina catalyst at about 2.7 megapascals to yield an equilibrium mixture of methanol, dimethyl ether, and water.
- This effluent is then mixed with synthesis gas and introduced into a reactor containing a zeolite catalyst (such as, for example, a ZSM-5 zeolite), at temperatures between about 35O 0 C and about 366 0 C and at pressures between about 1.9 megapascals and about 2.3 megapascals, to produce hydrocarbons and water.
- a zeolite catalyst such as, for example, a ZSM-5 zeolite
- the methanol-to-gas (MTG) reactions may be generally represented by Reactions [6], [7], and [8] below.
- Zeolites are substantially crystalline oxide materials in which the crystal structure of the oxide material defines pores, channels, or both pores and channels in the oxide material. Such pores and channels may have cross-sectional dimensions of between about 1 angstrom and about 200 angstroms, and typically have cross-sectional dimensions of between about 3 angstroms and about 15 angstroms.
- zeolite materials include metal atoms (classically, silicon or aluminum) that are surrounded by four oxygen anions to form an approximate tetrahedron consisting of a metal cation at the center of the tetrahedron and oxygen anions at the four apexes of the tetrahedron.
- the tetratrhedral metals are often referred to as "T-atoms.” These tetrahedrons then stack in substantially regular arrays to form channels. There are various ways in which the tetrahedrons may be stacked, and the resulting "frameworks" have been documented and categorized in, for example, Ch. Baerlocher, W.M. Meier and D.H. Olson, Atlas of Zeolite Framework Types, 5th ed., Elsevier: Amsterdam, 2001, the contents of which are hereby incorporated herein in their entirety by this reference.
- Silicon-based tetrahedrons in zeolitic materials are electrically neutral since silicon typically exhibits a 4+ oxidation state. Tetrahedrons based on elements other than silicon, however, may not be electrically neutral, and charge-compensating ions may be present so as to electrically neutralize the non-neutral tetrahedrons.
- many zeolites are aluminosilicates. Aluminum typically exists in the 3+ oxidation state, and charge-compensating cations typically populate the pores to maintain electrical neutrality. These charge-compensating cations may participate in ion-exchange processes. When the charge-compensating cations are protons, the zeolite may be a relatively strong solid acid. The acidic properties of such solid acid zeolites may contribute to their catalytic properties. Other types of reactive metal cations may also populate the pores to form catalytic materials with unique properties.
- the present invention includes a catalytic structure that includes a substantially crystalline zeolite material having a first plurality of pores and a second plurality of pores.
- the pores of the first plurality are substantially defined by interstitial spaces within the crystal structure of the substantially crystalline zeolite material.
- the pores of the second plurality are dispersed throughout the substantially crystalline zeolite material.
- a metallic material may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.
- a metal oxide material also may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.
- the present invention includes a catalytic structure that includes a zeolite material that is capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, and at least one catalytic material that is capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen disposed within the zeolite material.
- the zeolite material includes a first plurality of pores substantially defined by interstitial spaces within the crystal structure of the zeolite material, and a second plurality of pores dispersed throughout the zeolite material.
- the catalytic material may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.
- the present invention includes methods of fabricating catalytic structures.
- a zeolite material capable of catalyzing the formation of hydrocarbon molecules from methanol may be formed at least partially around at least one template structure.
- the template structure may be removed from within the zeolite material, and at least one catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen is introduced into the zeolite material.
- the present invention includes methods of synthesizing hydrocarbon molecules having two or more carbon atoms in which hydrogen and at least one of carbon monoxide and carbon dioxide are contacted with a catalytic structure.
- the catalytic structure includes a zeolite material that is capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, and at least one catalytic material that is capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen disposed within the zeolite material.
- the zeolite material includes a first plurality of pores substantially defined by interstitial spaces within the crystal structure of the zeolite material, and a second plurality of pores dispersed throughout the zeolite material.
- the catalytic material may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.
- the present invention includes systems for synthesizing hydrocarbon molecules from hydrogen and at least one of carbon monoxide and carbon dioxide.
- the systems include a catalytic structure disposed within a reactor.
- the catalytic structure includes a zeolite material that is capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, and at least one catalytic material that is capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen disposed within the zeolite material.
- the zeolite material includes a first plurality of pores substantially defined by interstitial spaces within the crystal structure of the zeolite material, and a second plurality of pores dispersed throughout the zeolite material.
- the catalytic material may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.
- FIG. 1 is a cross-sectional view of one example of a catalytic structure that embodies teachings of the present invention and includes a metal material and a metal oxide material that are disposed within pores of a zeolite material;
- FIG. 2 is a simplified illustration representing one example of a chemical structure framework that may be exhibited by the zeolite material shown in FIG. 1;
- FIG. 3 is an enlarged cross-sectional view of a pore extending through the zeolite material shown in FIG. 1 and illustrating catalytic material within the pore;
- FIGS. 4-7 illustrate one example of a method that may be used to fabricate a catalytic structure according to teachings of the present invention
- FIG. 8 is a partial cross-sectional view of a reactor that includes a catalytic structure that embodies teachings of the present invention.
- FIG. 9 is a partial cross-sectional view of a reactor that includes another catalytic structure that embodies teachings of the present invention.
- FIG. 10 is a schematic diagram of a system that embodies teachings of the present invention and includes a catalytic structure for catalyzing the formation of hydrocarbon molecules from hydrogen and at least one of carbon monoxide and carbon dioxide.
- zeolite material means and includes any substantially crystalline material in which the crystal structure of the material includes a plurality of interconnected tetrahedrons and has a framework density (FD) of between about 12 and about 23, wherein the framework density is defined as the number of tetrahedronally-coordinated atoms (T-atoms) per 1,000 cubic angstroms.
- zeolite materials include aluminosilicate-based materials, aluminophosphate-based materials, and silicoaluminophosphate-based materials.
- a zeolite material is an aluminosilicate- based material having a chemical structure in which the unit cell (smallest geometrically repeating unit of the crystal structure) is generally represented by the formula: M(y/n)[(A10 2 )y(Si0 2 )z] • (x)H 2 0, wherein M is a cation selected from elements in Group IA and Group HA of the Periodic Table of the Elements (including, for example, sodium, potassium, magnesium and calcium), n is the valence of the cations M, x is the number of water molecules per unit cell, y is the number of AlO 2 units per unit cell, and z is the number of SiO 2 units per unit cell.
- the ratio of z to y (z/y) may be any number greater than 1.
- a zeolite material is a silicoaluminophosphate-based material having a chemical structure in which the unite cell is generally represented by the formula:
- silicoaluminophosphate-based materials may also include a small amount of organic amine or quaternary ammonium templates, which are used to form the materials and retained therein.
- zeolite materials may further include additional elements and materials disposed within the interstitial spaces of the unit cell.
- pore means and includes any void in a material and includes voids of any size and shape.
- pores include generally spherical voids, generally rectangular voids, as well as elongated voids or channels having any cross-sectional shape including nonlinear or irregular shapes.
- micropore means and includes any void in a material having an average cross-sectional dimension of less than about 20 angstroms (2 nanometers).
- micropores include generally spherical pores having average diameter diameters of less than about 20 angstroms, as well as elongated channels having average cross-sectional dimensions of less than about 20 angstroms.
- mesopore means and includes any void in a material having an average cross-sectional dimension of greater than about 20 angstroms (2 nanometers) and less than about 500 angstroms (50 nanometers).
- mesopores include generally spherical pores having average diameters between about 20 angstroms and about 500 angstroms, as well as elongated channels having average cross-sectional dimensions between about 20 angstroms and about 500 angstroms.
- macropore means and includes any void in a material having an average cross-sectional dimension of greater than about 500 angstroms (50 nanometers).
- macropores include generally spherical pores having average diameters greater than about 500 angstroms, as well as elongated channels having average cross-sectional dimensions greater than about 500 angstroms.
- the catalytic structure 10 includes a zeolite material 12 that is capable of catalyzing the formation of hydrocarbon molecules having two or more hydrocarbons from methanol. As discussed in further detail below, the zeolite material 12 may have both a mesoporous structure and a microporous structure.
- the catalytic structure 10 may include a plurality of mesopores 14 dispersed throughout the zeolite material 12.
- the mesopores 14 may include elongated channels extending randomly through the zeolite material 12.
- some of the mesopores 14 may include an elongated pore having a generally cylindrical shape and an average cross-sectional diameter in a range extending from about 20 angstroms (2 nanometers) to about 500 angstroms (50 nanometers).
- Other mesopores 14 may be generally spherical and may have an average diameter in a range extending from about 20 angstroms (2 nanometers) to about 500 angstroms (50 nanometers).
- the mesopores 14 may be disposed in an ordered array within the zeolite material 12.
- the mesopores 14 may include elongated channels extending generally parallel to one another through the zeolite material 12.
- communication may be established between at least some of the mesopores 14.
- each mesopore 14 may be substantially isolated from other mesopores 14 by the zeolite material 12.
- the zeolite material 12 may include a plurality of macropores in addition to, or in place of, the plurality of mesopores 14.
- the zeolite material 12 may have an MFI framework type as defined in Ch. Baerlocher, W.M. Meier and D.H. Olson, Atlas of Zeolite Framework Types, 5th ed., Elsevier: Amsterdam, 2001. Furthermore, the zeolite material 12 may include an aluminosilicate-based material. By way of example and not limitation, the zeolite material 12 may include ZSM-5 zeolite material, which is an aluminosilicate-based zeolite material having an MFI framework type. Furthermore, the zeolite material 12 may be acidic.
- At least some metal cations of the zeolite material 12 may be replaced with hydrogen ions to provide a desired level of acidity to the zeolite material 12.
- Ion exchange reactions for replacing metal cations in a zeolite material with hydrogen ions are known in the art.
- FIG. 2 is an enlarged view of a portion of the zeolite material 12 shown in FIG. 1 and provides a simplified representation of the chemical structure framework of a zeolite material 12 having an MFI framework type, as viewed in the [010] direction.
- the zeolite material 12 may include a plurality of micropores 18 that extend through the zeolite material 12 and are substantially defined by the interstitial spaces within the crystal structure of the zeolite material 12.
- the micropores 18 shown in FIG. 2 may be substantially straight.
- the zeolite material 12 may further include additional micropores (not shown in FIG. 2) that extend through the zeolite material 12 in the [100] direction in a generally sinusoidal pattern.
- zeolite materials 12 are known in the art, and any zeolite material 12 that exhibits catalytic activity with respect to the formation of hydrocarbon molecules from methanol, as discussed in further detail below, may be used in catalytic structures that embody teachings of the present invention, such as the catalytic structure 10 shown in FIG. 1.
- the zeolite material 12 may include a silicoaluminophosphate-based material.
- the zeolite material 12 may have framework types other than MFI.
- the zeolite material 12 may have a BEA, FAU, MOR, FER, ERI, OFF, CHA or an AEI framework type.
- the zeolite material 12 may include SAPO-34 (CHA) or ALPO 4 -I8 (AEI).
- the catalytic structure 10 further includes an additional catalytic material disposed on and/or in the zeolite material 12.
- the additional catalytic material may be capable of catalyzing the formation of methanol from one or both of carbon monoxide (CO) and carbon dioxide (CO 2 ) in the presence of hydrogen.
- the catalytic structure 10 may include a first catalytic material 20 and a second catalytic material 22 disposed on interior and/or exterior surfaces of the zeolite material 12. As shown in FIG.
- the first catalytic material 20 and the second catalytic material 22 may be disposed within mesopores 14 of the zeolite material 12. It is contemplated that the first catalytic material 20, the second catalytic material 22, or both the first catalytic material 20 and the second catalytic material 22 also may be disposed within micropores 18 (FIG. 2) of the zeolite material 12.
- the first catalytic material 20 may form a coating extending over surfaces of the zeolite material 12 within the mesopores 14.
- the first catalytic material 20 may be configured as a plurality of nanoparticles disposed within the mesopores 14 of the zeolite material 12. Such nanoparticles may have an average diameter of, for example, less than about 500 angstroms (50 nanometers), and, more particularly, less than about 200 angstroms (20 nanometers).
- the second catalytic material 22 may form a coating extending over surfaces of the zeolite material 12 within the mesopores 14.
- the second catalytic material 22 may be configured as a plurality of nanoparticles disposed within mesopores 14 of the zeolite material 12.
- Such nanoparticles may have an average diameter of, for example, less than about 500 angstroms (50 nanometers), and, more particularly, less than about 200 angstroms (20 nanometers).
- first catalytic material 20 and the second catalytic material 22 each may comprise regions of a single layer or coating extending over surfaces of the zeolite material 12 within the mesopores 14. In some embodiments of the present invention, one or both of the first catalytic material
- first catalytic material 20 and the second catalytic material 22 may be chemically bound to the zeolite material 12 by, for example, a chemical complex or a chemical bond.
- first catalytic material 20 and the second catalytic material 22 may be physically bound to the zeolite material 12 by mechanical interference between surfaces of the zeolite material 12 and conformal layers of one or both of the first catalytic material 20 and the second catalytic material 22 formed over such surfaces of the zeolite material 12.
- nanoparticles of one or both of the first catalytic material 20 and the second catalytic material 22 may be generally loosely disposed within the mesopores 14 of the zeolite material 12.
- the first catalytic material 20 and the second catalytic material 22 may be capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen.
- the first catalytic material 20 may include a metallic material such as, for example, copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium (including alloys based on one or more of such metallic materials).
- the second catalytic material 22 may include a metal oxide material such as, for example, zinc oxide, magnesium oxide, zirconium oxide, iron oxide, or tungsten oxide.
- a plurality of template structures 30 may be provided within a container 32.
- the template structures 30 may have a selected size and shape corresponding to a desired size and shape of pores, such as, for example, the mesopores 14 (FIG. 1), to be formed in the catalytic structure 10.
- the template structures 30 may comprise nanoparticles, nano wires, or nanotubes.
- the template structures 30 may be formed from or include any material that may be subsequently removed from a zeolite material 12 formed around the template structures 30 without significantly damaging or otherwise affecting the zeolite material 12.
- the template structures 30 may include carbon.
- the template structures 30 include carbon nanowires. Each carbon nanowire may be generally cylindrical and may have an average cross- sectional diameter between about 10 angstroms (1 nanometer) and about 2,000 angstroms (200 nanometers).
- the template structures 30 may include carbon nanoparticles, carbon nanotubes, or a mixture of at least two of carbon nanowires, nanoparticles, and nanotubes. Furthermore, the template structures 30 optionally may be formed from or include materials other than carbon such as, for example, any polymer material allowing the formation of a zeolite material 12 around the template structures 30 and subsequent removal of the polymer material from the zeolite material 12 without significantly damaging or otherwise affecting the zeolite material 12.
- a zeolite material 12 may be formed around the template structures 30 using methods known in the art, such as, for example, those methods described in U.S. Patent No. 3,702,886 to Argauer et al., the entire disclosure of which is incorporated herein in its entirety by this reference.
- the template structures 30 may be removed from within the zeolite material 12 to form mesopores 14 (and optionally macropores), as shown in FIG. 6.
- the carbon material may be removed by, for example, calcining in air.
- the zeolite material 12 and the template structures 30 may be heated in air to temperatures of about 600 0 C for about 20 hours to calcine the carbon material.
- the first catalytic material 20 and the second catalytic material 22 may be provided on and/or in the zeolite material 12.
- particles of the first catalytic material 20 and particles of the second catalytic material 22 may be suspended in a liquid.
- the liquid and the particles of the first catalytic material 20 and the second catalytic material 22 may be provided within the mesopores 14 of the zeolite material 12 by, for example, immersing the zeolite material 12 in the liquid suspension.
- the zeolite material 12 then may be removed from the liquid suspension and allowed to dry (at ambient or elevated temperatures) to remove the liquid from the liquid suspension, leaving behind the particles of the first catalytic material 20 and the second catalytic material 22 within the mesopores 14 of the zeolite material 12.
- the first catalytic material 20 and the second catalytic material 22 may be provided on and/or in the zeolite material 12 by precipitation of their respective metal salts (i.e., nitrates or acetates).
- the precursor salts may be provided in the mesopores 14 of the zeolite material 12 using, for example, the incipient wetness technique.
- the precursor salts then may be precipitated using standard reagents such as, for example, ammonia or sodium hydroxide.
- the first catalytic material 20 may include copper and the second catalytic material 22 may include zinc oxide.
- One method by which copper and zinc oxide may be provided within mesopores 14 of the zeolite material 12 is to immerse the zeolite material 12 in a nitrate solution comprising copper nitrate (Cu(NC ⁇ ) 2 ) and zinc nitrate (Zn(NC ⁇ ) 2 ).
- the zeolite material 12 may be first immersed in one of a copper nitrate solution and a zinc nitrate solution, and subsequently immersed in the other of the copper nitrate solution and the zinc nitrate solution.
- the zeolite material 12 may be dried after immersion in the first nitrate solution and prior to immersion in the second nitrate solution.
- the copper nitrate and zinc nitrate on and within the zeolite material 12 then may converted to copper oxide (CuO) and zinc oxide (ZnO) by, for example, heating the zeolite material 12 in air to temperatures between about 100 0 C and about 25O 0 C.
- the copper oxide (CuO) then may be converted to copper (Cu) by, for example, flowing hydrogen gas (H 2 ) over the zeolite material 12 at elevated temperatures (for example, about 24O 0 C).
- the first catalytic material 20 and the second catalytic material 22 may be provided on and/or in the zeolite material 12 by preparing a first aqueous solution of zinc nitrate and copper nitrate and adding the zeolite material 12 to the aqueous solution.
- An additional solution may be prepared that includes hexamethylenetetramine and sodium citrate. This additional solution may be added to the first aqueous solution, and the mixture may be heated in a closed vessel, such as, for example, a Parr acid digestion bomb, to between about 95 0 C and about 120 for between about one hour and about four hours.
- the sample then may be filtered, washed, and dried.
- the sample then may be oxidized in air at temperatures between about 100 0 C and about 25O 0 C to form the copper oxide and zinc oxide, after which the copper oxide may be converted to copper as described above.
- the template structures 30 shown in FIG. 4 may include carbon nanotubes.
- the carbon nanotubes may be impregnated with a solution comprising copper nitrate and zinc nitrate. After forming the zeolite material 12 around the impregnated carbon nanotubes, the carbon nanotubes may be removed by calcining in air, as previously described, and copper and zinc oxide may be formed from the copper nitrate and the zinc nitrate, respectively, as the carbon nanotubes are calcined in the air. Referring to FIG.
- the above described method may be used to provide the first catalytic material 20, which may include copper (Cu), and the second catalytic material 22, which may include zinc oxide (ZnO), within mesopores 14 of the zeolite material 12 (and optionally within micropores 18 and/or macropores of the zeolite material 12) and to form the catalytic structure 10.
- the catalytic structure 10 may include a quantity of powder 48 comprising relatively fine particles.
- the particles of the powder 48 may include first and second catalytic materials 20, 22 disposed within a zeolite material 12, as previously described in relation to FIGS. 1-3.
- the powder 48 may be provided within a container 40 having an inlet 42 and an outlet 44, and the powder 48 may be disposed between the inlet 42 and the outlet 44.
- a gas comprising hydrogen and at least one of carbon monoxide (CO) and carbon dioxide (CO 2 ) may be introduced into the container 40 through the inlet 42.
- the powder 48 may catalyze the formation of hydrocarbon molecules having two or more carbon atoms from the carbon monoxide (CO) and carbon dioxide (CO 2 ).
- the first catalytic material 20 and the second catalytic material 22 (FIG.
- zeolite material 12 may catalyze the formation of hydrocarbon molecules having two or more carbon atoms from the methanol.
- the hydrocarbon molecules may be collected from the outlet 44 of the container 40 and purified and/or concentrated as necessary or desired.
- the catalytic structure 10 may include a plurality of particles, briquettes, or pellets 50, each of which includes first and second catalytic materials 20, 22 disposed within a zeolite material 12, as previously described in relation to FIGS. 1-3.
- the pellets 50 may be formed by pressing the powder 48 previously described in relation to FIG. 8 in a die or mold to form the pellets 50.
- the plurality of pellets 50 may be provided within a container 40, as shown in FIG. 9.
- a gas comprising at least one of carbon monoxide (CO) and carbon dioxide (CO 2 ) may be introduced into the container 40 through the inlet 42, and the pellets 50 may catalyze the formation of hydrocarbon molecules having two or more carbon atoms from hydrogen and the carbon monoxide (CO) and/or carbon dioxide (CO 2 ), as previously described in relation to FIG. 8.
- FIG. 10 is a simplified schematic of a system 60 that embodies teachings of the present invention and that may be used to form hydrocarbon molecules having two or more carbon atoms from carbon monoxide (CO) and/or carbon dioxide (CO 2 ) in the presence of hydrogen using a catalytic structure that embodies teachings of the present invention, such as, for example, the catalytic structure 10 previously described in relation to FIGS. 1-3.
- the system 60 may include a reactor 40, a gas-liquid separator 64, and a compressor 66.
- the reactor 40 may include a catalytic structure that embodies teachings of the present invention, such as, for example, the catalytic structure 10.
- the system 60 may further include a first heat exchanger 68A for heating a reactant mixture fed to the reactor 40, and a second heat exchanger 68B for cooling products (and any unreacted reactants and/or reaction byproducts) as they exit the reactor 40.
- the system 60 may further include a heating device (not shown) for heating the reactor 40 and the catalytic structure 10 to elevated temperatures.
- a heating device may be configured to heat the reactor 40 and the catalytic structure 10 to a temperature between about 200 0 C and about 500 0 C.
- the reactor 40 may be pressurized to between about 0.5 megapascals (5 atmospheres) and about 10 megapascals (100 atmospheres).
- a reactant mixture 70 that includes hydrogen gas and at least one of carbon monoxide (CO) and carbon dioxide (CO 2 ) may be passed through the first heat exchanger 68A and fed to the reactor 40.
- the catalytic structure 10 may catalyze the formation of hydrocarbon molecules having two or more carbon atoms from the hydrogen and carbon monoxide (CO) and/or carbon dioxide (CO 2 ).
- a product mixture 72 (which may include such hydrocarbon molecules), together with any unreacted reactant gasses 74 and reaction byproducts, may be collected from the reactor 40 and passed through the second heat exchanger 68B to the gas-liquid separator 64.
- the gas liquid separator 64 may be used to separate liquid hydrocarbon products of the product mixture 72 from the unreacted reactant gases 74.
- the unreacted reactant gasses 74 may be re-pressurized as necessary using the compressor 66 and recombined with the reactant mixture 70 through the three-way valve 78, as shown in FIG. 10.
- the liquid hydrocarbon products in the product mixture 72 collected from the gas-liquid separator 64 may then be further processed as necessary or desired.
- additional distillation equipment (not shown) may be used to purify and concentrate the various hydrocarbon components in the product mixture 72 as necessary or desired.
- the catalytic structures, systems, and methods described herein may be used to catalyze the conversion of hydrogen and at least one of carbon monoxide and carbon dioxide to hydrocarbons having two or more carbon atoms with improved catalytic activity and selectivity relative to known catalytic structures, systems, and methods.
- the catalytic structures, systems, and methods described herein may facilitate economic utilization of carbon dioxide from stationary carbon dioxide sources, such as coal-powered and hydrocarbon-powered electricity generation plants, which otherwise may be vented to atmosphere.
- the methods described herein may be used to fabricate various catalytic structures, other than those described herein, that include a bi-modal (microporous and mesorporous) or multi-modal (microporous, mesoporous, and macroporous) zeolite material and a metal and/or metal oxide catalyst material disposed on and/or in the zeolite material.
- Such catalytic structures may be bi- functional.
- the zeolite material itself may function as one catalytic material, while the catalytic material disposed on and/or in the zeolite material may function as a second catalytic material.
- bi-functional catalytic structures may be useful in many additional applications where it is necessary or desirable to provide different catalytic functions to a single catalytic structure or material.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing the formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing the formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by the crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.
Description
TITLE OF THE INVENTION
STRUCTURES INCLUDING CATALYTIC MATERIALS DISPOSED WITHIN
POROUS ZEOLITE MATERIALS, SYSTEMS AND METHODS FOR USING THE
SAME, AND METHODS OF FABRICATING CATALYTIC STRUCTURES
RELATED APPLICATIONS
This application claims benefit of U.S. Non-provisional application No. 11/464,566, filed August 15, 2006, entitled HIGH CAPACITY ADSORPTION MEDIA FOR SEPARATING OR REMOVING CONSTITUENTS, ASSOCIATED APPARATUS, AND METHODS OF PRODUCING AND USING THE ADSORPTION MEDIA, which is incorporated herein by reference in its entirety.
GOVERNMENT RIGHTS
The United States Government has certain rights in this invention pursuant to Contract No. DE-AC07-05ID14517 between the United States Department of Energy and Battelle Energy Alliance, LLC.
FIELD OF THE INVENTION
The present invention relates to catalytic materials, structures, systems, and methods. More particularly, the present invention relates to catalytic structures including zeolite materials, and to systems and methods for synthesizing hydrocarbon molecules from hydrogen and at least one of carbon monoxide and carbon dioxide using such catalytic structures. The present invention also relates to methods of fabricating catalytic structures that include zeolite materials.
BACKGROUND OF THE INVENTION
Carbon dioxide gas (CO2) may be converted into liquid fuels such as, for example, hydrocarbon molecules of between about 5 and about 12 carbon atoms per molecule (e.g., gasoline) through multi-step reactions. For example, carbon dioxide (CO2) gas and hydrogen (H2) may be converted to carbon monoxide (CO) gas and water (H2O) through the Reverse Water-Gas Shift Reaction, which is shown by Reaction [1] below.
[1] CO2 + H2 → CO + H2O
Synthesis gas, which is a mixture of carbon monoxide gas (CO) and hydrogen gas (H2) then may be produced from the reaction products of the Reverse Water-Gas Shift Reaction by adding additional hydrogen gas (H2) to the reaction products. This synthesis gas may be further
reacted through either Fischer-Tropsch (FT) processes, or through methanol synthesis (MS) plus methanol-to-gasoline (MTG) processes, to provide liquid fuels.
Briefly, Fischer-Tropsch processes include various catalyzed chemical reactions in which synthesis gas is converted into liquid hydrocarbons in a reactor in the presence of a catalyst and at temperatures between about 2000C and about 35O0C. Catalysts used in Fischer- Tropsch processes include, for example, iron, cobalt, nickel, and ruthenium. While various interrelated reactions may occur in Fischer-Tropsch processes, the overall reaction process may be generally represented by Reaction [2] below.
[2] (2n + I)H2 + nCO → CnH2n+2 + nH20 As mentioned above, synthesis gas may also be reacted by first performing a methanol synthesis (MS) process, and then performing a methanol-to-gasoline (MTG) process to produce liquid fuels. Methanol synthesis (MS) processes involve the catalytic conversion of carbon monoxide, carbon dioxide, hydrogen, and water to methanol and other reaction byproducts. The methanol synthesis reactions may be generally represented by Reactions [3], [4], and [5] below. [3] CO + 2H2 → CH3OH
[4] CO2 + 3H2 → CH3OH + H2O
[5] CO + H2O → CO2 + H2
The methanol-to-gas (MTG) process involves the conversion of methanol to hydrocarbon molecules using zeolite catalysts, which are described in further detail below. The methanol-to-gas (MTG) process occurs in two steps. First, methanol is heated to about 3000C and partially dehydrated over an alumina catalyst at about 2.7 megapascals to yield an equilibrium mixture of methanol, dimethyl ether, and water. This effluent is then mixed with synthesis gas and introduced into a reactor containing a zeolite catalyst (such as, for example, a ZSM-5 zeolite), at temperatures between about 35O0C and about 3660C and at pressures between about 1.9 megapascals and about 2.3 megapascals, to produce hydrocarbons and water. The methanol-to-gas (MTG) reactions may be generally represented by Reactions [6], [7], and [8] below.
[6] 2CH3OH → CH3OCH3 + H2O
[7] CH3OCH3 → C2-C5 Olefins [8] C2-C5 Olefins — > Paraffins, Cycloparaffins, Aromatics
While the feasibility of the above-described reactions has been demonstrated, mass production of liquid fuels using such processes has not been widely implemented due, at least in part, to the relatively high costs associated with carrying out the reactions, and to the relatively low yields exhibited by the reactions.
In an effort to improve the yield of the various reactions and to minimize the costs associated with carrying out the reactions, research has been conducted in an effort to improve the efficiency of the catalysts associated with each of the respective catalyzed reactions. As previously mentioned, zeolites have been used as catalysts in the methanol-to-gas (MTG) process.
Zeolites are substantially crystalline oxide materials in which the crystal structure of the oxide material defines pores, channels, or both pores and channels in the oxide material. Such pores and channels may have cross-sectional dimensions of between about 1 angstrom and about 200 angstroms, and typically have cross-sectional dimensions of between about 3 angstroms and about 15 angstroms. Typically, zeolite materials include metal atoms (classically, silicon or aluminum) that are surrounded by four oxygen anions to form an approximate tetrahedron consisting of a metal cation at the center of the tetrahedron and oxygen anions at the four apexes of the tetrahedron. The tetratrhedral metals are often referred to as "T-atoms." These tetrahedrons then stack in substantially regular arrays to form channels. There are various ways in which the tetrahedrons may be stacked, and the resulting "frameworks" have been documented and categorized in, for example, Ch. Baerlocher, W.M. Meier and D.H. Olson, Atlas of Zeolite Framework Types, 5th ed., Elsevier: Amsterdam, 2001, the contents of which are hereby incorporated herein in their entirety by this reference.
Silicon-based tetrahedrons in zeolitic materials are electrically neutral since silicon typically exhibits a 4+ oxidation state. Tetrahedrons based on elements other than silicon, however, may not be electrically neutral, and charge-compensating ions may be present so as to electrically neutralize the non-neutral tetrahedrons. For example, many zeolites are aluminosilicates. Aluminum typically exists in the 3+ oxidation state, and charge-compensating cations typically populate the pores to maintain electrical neutrality. These charge-compensating cations may participate in ion-exchange processes. When the charge-compensating cations are protons, the zeolite may be a relatively strong solid acid. The acidic properties of such solid acid zeolites may contribute to their catalytic properties. Other types of reactive metal cations may also populate the pores to form catalytic materials with unique properties.
Notwithstanding the research that has been conducted with respect to the above- described reactions and their respective catalytic materials, there remains a need in the art for catalytic materials and structures that can be used to provide a direct route or mechanism for the reduction of carbon monoxide (CO) and/or carbon dioxide (CO2) to liquid fuels.
BRIEF SUMMARY OF THE INVENTION
In one example embodiment, the present invention includes a catalytic structure that includes a substantially crystalline zeolite material having a first plurality of pores and a second plurality of pores. The pores of the first plurality are substantially defined by interstitial spaces within the crystal structure of the substantially crystalline zeolite material. The pores of the second plurality are dispersed throughout the substantially crystalline zeolite material. A metallic material may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores. A metal oxide material also may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores. In another example embodiment, the present invention includes a catalytic structure that includes a zeolite material that is capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, and at least one catalytic material that is capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen disposed within the zeolite material. The zeolite material includes a first plurality of pores substantially defined by interstitial spaces within the crystal structure of the zeolite material, and a second plurality of pores dispersed throughout the zeolite material. The catalytic material may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.
In an additional example embodiment, the present invention includes methods of fabricating catalytic structures. A zeolite material capable of catalyzing the formation of hydrocarbon molecules from methanol may be formed at least partially around at least one template structure. The template structure may be removed from within the zeolite material, and at least one catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen is introduced into the zeolite material.
In yet a further example embodiment, the present invention includes methods of synthesizing hydrocarbon molecules having two or more carbon atoms in which hydrogen and at least one of carbon monoxide and carbon dioxide are contacted with a catalytic structure. The catalytic structure includes a zeolite material that is capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, and at least one catalytic material that is capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen disposed within the zeolite material. The zeolite material includes a first plurality of pores substantially defined by interstitial spaces within the crystal structure of the zeolite material, and a second plurality of
pores dispersed throughout the zeolite material. The catalytic material may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.
In still another example embodiment, the present invention includes systems for synthesizing hydrocarbon molecules from hydrogen and at least one of carbon monoxide and carbon dioxide. The systems include a catalytic structure disposed within a reactor. The catalytic structure includes a zeolite material that is capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, and at least one catalytic material that is capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen disposed within the zeolite material. The zeolite material includes a first plurality of pores substantially defined by interstitial spaces within the crystal structure of the zeolite material, and a second plurality of pores dispersed throughout the zeolite material. The catalytic material may be disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
While the specification concludes with claims particularly pointing out and distinctly claiming that which is regarded as the present invention, the advantages of this invention may be more readily ascertained from the following description of the invention when read in conjunction with the accompanying drawings in which: FIG. 1 is a cross-sectional view of one example of a catalytic structure that embodies teachings of the present invention and includes a metal material and a metal oxide material that are disposed within pores of a zeolite material;
FIG. 2 is a simplified illustration representing one example of a chemical structure framework that may be exhibited by the zeolite material shown in FIG. 1; FIG. 3 is an enlarged cross-sectional view of a pore extending through the zeolite material shown in FIG. 1 and illustrating catalytic material within the pore;
FIGS. 4-7 illustrate one example of a method that may be used to fabricate a catalytic structure according to teachings of the present invention;
FIG. 8 is a partial cross-sectional view of a reactor that includes a catalytic structure that embodies teachings of the present invention;
FIG. 9 is a partial cross-sectional view of a reactor that includes another catalytic structure that embodies teachings of the present invention; and
FIG. 10 is a schematic diagram of a system that embodies teachings of the present invention and includes a catalytic structure for catalyzing the formation of hydrocarbon molecules from hydrogen and at least one of carbon monoxide and carbon dioxide.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the term "zeolite material" means and includes any substantially crystalline material in which the crystal structure of the material includes a plurality of interconnected tetrahedrons and has a framework density (FD) of between about 12 and about 23, wherein the framework density is defined as the number of tetrahedronally-coordinated atoms (T-atoms) per 1,000 cubic angstroms. By way of example and not limitation, zeolite materials include aluminosilicate-based materials, aluminophosphate-based materials, and silicoaluminophosphate-based materials. An example of a zeolite material is an aluminosilicate- based material having a chemical structure in which the unit cell (smallest geometrically repeating unit of the crystal structure) is generally represented by the formula: M(y/n)[(A102)y(Si02)z] • (x)H20, wherein M is a cation selected from elements in Group IA and Group HA of the Periodic Table of the Elements (including, for example, sodium, potassium, magnesium and calcium), n is the valence of the cations M, x is the number of water molecules per unit cell, y is the number of AlO2 units per unit cell, and z is the number of SiO2 units per unit cell. In some zeolite materials, the ratio of z to y (z/y) may be any number greater than 1. Another example of a zeolite material is a silicoaluminophosphate-based material having a chemical structure in which the unite cell is generally represented by the formula:
(SiaAlbPc)O2 • (x)H20 wherein x is the number of water molecules per unit cell, z is the number of silicon atoms per unit cell, b is the number of aluminum atoms per unit cell, and c is the number of phosphorous atoms per unit cell. Such silicoaluminophosphate-based materials may also include a small amount of organic amine or quaternary ammonium templates, which are used to form the materials and retained therein. Such zeolite materials may further include additional elements and materials disposed within the interstitial spaces of the unit cell. As used herein, the term "pore" means and includes any void in a material and includes voids of any size and shape. For example, pores include generally spherical voids, generally rectangular voids, as well as elongated voids or channels having any cross-sectional shape including nonlinear or irregular shapes.
As used herein, the term "micropore" means and includes any void in a material having an average cross-sectional dimension of less than about 20 angstroms (2 nanometers). For example, micropores include generally spherical pores having average diameter diameters of less than about 20 angstroms, as well as elongated channels having average cross-sectional dimensions of less than about 20 angstroms.
As used herein, the term "mesopore" means and includes any void in a material having an average cross-sectional dimension of greater than about 20 angstroms (2 nanometers) and less than about 500 angstroms (50 nanometers). For example, mesopores include generally spherical pores having average diameters between about 20 angstroms and about 500 angstroms, as well as elongated channels having average cross-sectional dimensions between about 20 angstroms and about 500 angstroms.
As used herein, the term "macropore" means and includes any void in a material having an average cross-sectional dimension of greater than about 500 angstroms (50 nanometers). For example, macropores include generally spherical pores having average diameters greater than about 500 angstroms, as well as elongated channels having average cross-sectional dimensions greater than about 500 angstroms.
The illustrations presented herein are not meant to be actual views of any particular catalytic structure, reactor, or system, but are merely idealized representations which are employed to describe the present invention. Additionally, elements common between figures may retain the same numerical designation.
One example of a catalytic structure 10 that embodies teachings of the present invention is shown in FIG. 1. The catalytic structure 10 includes a zeolite material 12 that is capable of catalyzing the formation of hydrocarbon molecules having two or more hydrocarbons from methanol. As discussed in further detail below, the zeolite material 12 may have both a mesoporous structure and a microporous structure.
Referring to FIG. 1, the catalytic structure 10 may include a plurality of mesopores 14 dispersed throughout the zeolite material 12. The mesopores 14 may include elongated channels extending randomly through the zeolite material 12. By way of example and not limitation, some of the mesopores 14 may include an elongated pore having a generally cylindrical shape and an average cross-sectional diameter in a range extending from about 20 angstroms (2 nanometers) to about 500 angstroms (50 nanometers). Other mesopores 14 may be generally spherical and may have an average diameter in a range extending from about 20 angstroms (2 nanometers) to about 500 angstroms (50 nanometers). In additional embodiments, the mesopores 14 may be disposed in an ordered array within the zeolite material 12. For example,
the mesopores 14 may include elongated channels extending generally parallel to one another through the zeolite material 12. In some embodiments, communication may be established between at least some of the mesopores 14. In additional embodiments, each mesopore 14 may be substantially isolated from other mesopores 14 by the zeolite material 12. Furthermore, the zeolite material 12 may include a plurality of macropores in addition to, or in place of, the plurality of mesopores 14.
In one embodiment of the present invention, the zeolite material 12 may have an MFI framework type as defined in Ch. Baerlocher, W.M. Meier and D.H. Olson, Atlas of Zeolite Framework Types, 5th ed., Elsevier: Amsterdam, 2001. Furthermore, the zeolite material 12 may include an aluminosilicate-based material. By way of example and not limitation, the zeolite material 12 may include ZSM-5 zeolite material, which is an aluminosilicate-based zeolite material having an MFI framework type. Furthermore, the zeolite material 12 may be acidic. For example, at least some metal cations of the zeolite material 12 may be replaced with hydrogen ions to provide a desired level of acidity to the zeolite material 12. Ion exchange reactions for replacing metal cations in a zeolite material with hydrogen ions are known in the art.
FIG. 2 is an enlarged view of a portion of the zeolite material 12 shown in FIG. 1 and provides a simplified representation of the chemical structure framework of a zeolite material 12 having an MFI framework type, as viewed in the [010] direction. As shown therein, the zeolite material 12 may include a plurality of micropores 18 that extend through the zeolite material 12 and are substantially defined by the interstitial spaces within the crystal structure of the zeolite material 12. The micropores 18 shown in FIG. 2 may be substantially straight. The zeolite material 12 may further include additional micropores (not shown in FIG. 2) that extend through the zeolite material 12 in the [100] direction in a generally sinusoidal pattern. Various types of zeolite materials 12 are known in the art, and any zeolite material 12 that exhibits catalytic activity with respect to the formation of hydrocarbon molecules from methanol, as discussed in further detail below, may be used in catalytic structures that embody teachings of the present invention, such as the catalytic structure 10 shown in FIG. 1. For example, the zeolite material 12 may include a silicoaluminophosphate-based material. Furthermore, the zeolite material 12 may have framework types other than MFI. By way of example and not limitation, the zeolite material 12 may have a BEA, FAU, MOR, FER, ERI, OFF, CHA or an AEI framework type. By way of example and not limitation, the zeolite material 12 may include SAPO-34 (CHA) or ALPO4-I8 (AEI).
Referring to FIG. 3, the catalytic structure 10 further includes an additional catalytic material disposed on and/or in the zeolite material 12. The additional catalytic material may be capable of catalyzing the formation of methanol from one or both of carbon monoxide (CO) and carbon dioxide (CO2) in the presence of hydrogen. For example, the catalytic structure 10 may include a first catalytic material 20 and a second catalytic material 22 disposed on interior and/or exterior surfaces of the zeolite material 12. As shown in FIG. 3, the first catalytic material 20 and the second catalytic material 22 may be disposed within mesopores 14 of the zeolite material 12. It is contemplated that the first catalytic material 20, the second catalytic material 22, or both the first catalytic material 20 and the second catalytic material 22 also may be disposed within micropores 18 (FIG. 2) of the zeolite material 12.
In some embodiments, the first catalytic material 20 may form a coating extending over surfaces of the zeolite material 12 within the mesopores 14. In additional embodiments, the first catalytic material 20 may be configured as a plurality of nanoparticles disposed within the mesopores 14 of the zeolite material 12. Such nanoparticles may have an average diameter of, for example, less than about 500 angstroms (50 nanometers), and, more particularly, less than about 200 angstroms (20 nanometers). Similarly, the second catalytic material 22 may form a coating extending over surfaces of the zeolite material 12 within the mesopores 14. In additional embodiments, the second catalytic material 22 may be configured as a plurality of nanoparticles disposed within mesopores 14 of the zeolite material 12. Such nanoparticles may have an average diameter of, for example, less than about 500 angstroms (50 nanometers), and, more particularly, less than about 200 angstroms (20 nanometers).
In yet additional embodiments, the first catalytic material 20 and the second catalytic material 22 each may comprise regions of a single layer or coating extending over surfaces of the zeolite material 12 within the mesopores 14. In some embodiments of the present invention, one or both of the first catalytic material
20 and the second catalytic material 22 may be chemically bound to the zeolite material 12 by, for example, a chemical complex or a chemical bond. In additional embodiments, the first catalytic material 20 and the second catalytic material 22 may be physically bound to the zeolite material 12 by mechanical interference between surfaces of the zeolite material 12 and conformal layers of one or both of the first catalytic material 20 and the second catalytic material 22 formed over such surfaces of the zeolite material 12. In yet other embodiments, there may be substantially no chemical or physical bond between the zeolite material 12 and one or both of the first catalytic material 20 and the second catalytic material 22. For example, nanoparticles of
one or both of the first catalytic material 20 and the second catalytic material 22 may be generally loosely disposed within the mesopores 14 of the zeolite material 12.
As previously mentioned, the first catalytic material 20 and the second catalytic material 22 may be capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen. By way of example and not limitation, the first catalytic material 20 may include a metallic material such as, for example, copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium (including alloys based on one or more of such metallic materials). By way of example and not limitation, the second catalytic material 22 may include a metal oxide material such as, for example, zinc oxide, magnesium oxide, zirconium oxide, iron oxide, or tungsten oxide.
One example of a method that may be used to form catalytic structures that embody teachings of the present invention, such as, for example, the catalytic structure 10 shown in FIGS. 1-3, will now be described with reference to FIGS. 4-7.
Referring to FIG. 4, a plurality of template structures 30 may be provided within a container 32. The template structures 30 may have a selected size and shape corresponding to a desired size and shape of pores, such as, for example, the mesopores 14 (FIG. 1), to be formed in the catalytic structure 10. By way of example and not limitation, the template structures 30 may comprise nanoparticles, nano wires, or nanotubes. The template structures 30 may be formed from or include any material that may be subsequently removed from a zeolite material 12 formed around the template structures 30 without significantly damaging or otherwise affecting the zeolite material 12. By way of example and not limitation, the template structures 30 may include carbon. In the embodiment shown in FIG. 4, the template structures 30 include carbon nanowires. Each carbon nanowire may be generally cylindrical and may have an average cross- sectional diameter between about 10 angstroms (1 nanometer) and about 2,000 angstroms (200 nanometers).
In additional embodiments, the template structures 30 may include carbon nanoparticles, carbon nanotubes, or a mixture of at least two of carbon nanowires, nanoparticles, and nanotubes. Furthermore, the template structures 30 optionally may be formed from or include materials other than carbon such as, for example, any polymer material allowing the formation of a zeolite material 12 around the template structures 30 and subsequent removal of the polymer material from the zeolite material 12 without significantly damaging or otherwise affecting the zeolite material 12.
Referring to FIG. 5, a zeolite material 12 may be formed around the template structures 30 using methods known in the art, such as, for example, those methods described in U.S. Patent
No. 3,702,886 to Argauer et al., the entire disclosure of which is incorporated herein in its entirety by this reference.
After forming the zeolite material 12 around the template structures 30, the template structures 30 may be removed from within the zeolite material 12 to form mesopores 14 (and optionally macropores), as shown in FIG. 6. If the template structures 30 comprise carbon material, the carbon material may be removed by, for example, calcining in air. By way of example and not limitation, the zeolite material 12 and the template structures 30 may be heated in air to temperatures of about 600 0C for about 20 hours to calcine the carbon material.
After removing the template structures 30 from within the zeolite material 12 to form the mesopores 14 (and optionally macropores), the first catalytic material 20 and the second catalytic material 22 may be provided on and/or in the zeolite material 12.
By way of example and not limitation, particles of the first catalytic material 20 and particles of the second catalytic material 22 (or precursor materials from which the first catalytic material 20 and the second catalytic material 22 can be subsequently formed) may be suspended in a liquid. The liquid and the particles of the first catalytic material 20 and the second catalytic material 22 may be provided within the mesopores 14 of the zeolite material 12 by, for example, immersing the zeolite material 12 in the liquid suspension. The zeolite material 12 then may be removed from the liquid suspension and allowed to dry (at ambient or elevated temperatures) to remove the liquid from the liquid suspension, leaving behind the particles of the first catalytic material 20 and the second catalytic material 22 within the mesopores 14 of the zeolite material 12.
As another example, the first catalytic material 20 and the second catalytic material 22 may be provided on and/or in the zeolite material 12 by precipitation of their respective metal salts (i.e., nitrates or acetates). The precursor salts may be provided in the mesopores 14 of the zeolite material 12 using, for example, the incipient wetness technique. The precursor salts then may be precipitated using standard reagents such as, for example, ammonia or sodium hydroxide. As previously discussed herein, in one embodiment of the present invention, the first catalytic material 20 may include copper and the second catalytic material 22 may include zinc oxide. One method by which copper and zinc oxide may be provided within mesopores 14 of the zeolite material 12 is to immerse the zeolite material 12 in a nitrate solution comprising copper nitrate (Cu(NC^)2) and zinc nitrate (Zn(NC^)2 ). In additional embodiments, the zeolite material 12 may be first immersed in one of a copper nitrate solution and a zinc nitrate solution, and subsequently immersed in the other of the copper nitrate solution and the zinc nitrate
solution. Furthermore, the zeolite material 12 may be dried after immersion in the first nitrate solution and prior to immersion in the second nitrate solution.
The copper nitrate and zinc nitrate on and within the zeolite material 12 then may converted to copper oxide (CuO) and zinc oxide (ZnO) by, for example, heating the zeolite material 12 in air to temperatures between about 1000C and about 25O0C. The copper oxide (CuO) then may be converted to copper (Cu) by, for example, flowing hydrogen gas (H2) over the zeolite material 12 at elevated temperatures (for example, about 24O0C).
As yet another example, the first catalytic material 20 and the second catalytic material 22 may be provided on and/or in the zeolite material 12 by preparing a first aqueous solution of zinc nitrate and copper nitrate and adding the zeolite material 12 to the aqueous solution. An additional solution may be prepared that includes hexamethylenetetramine and sodium citrate. This additional solution may be added to the first aqueous solution, and the mixture may be heated in a closed vessel, such as, for example, a Parr acid digestion bomb, to between about 950C and about 120 for between about one hour and about four hours. The sample then may be filtered, washed, and dried. The sample then may be oxidized in air at temperatures between about 1000C and about 25O0C to form the copper oxide and zinc oxide, after which the copper oxide may be converted to copper as described above.
In an additional method that embodies teachings of the present invention, the template structures 30 shown in FIG. 4 may include carbon nanotubes. The carbon nanotubes may be impregnated with a solution comprising copper nitrate and zinc nitrate. After forming the zeolite material 12 around the impregnated carbon nanotubes, the carbon nanotubes may be removed by calcining in air, as previously described, and copper and zinc oxide may be formed from the copper nitrate and the zinc nitrate, respectively, as the carbon nanotubes are calcined in the air. Referring to FIG. 7, the above described method may be used to provide the first catalytic material 20, which may include copper (Cu), and the second catalytic material 22, which may include zinc oxide (ZnO), within mesopores 14 of the zeolite material 12 (and optionally within micropores 18 and/or macropores of the zeolite material 12) and to form the catalytic structure 10. Referring to FIG. 8, in some embodiments of the present invention, the catalytic structure 10 may include a quantity of powder 48 comprising relatively fine particles. The particles of the powder 48 may include first and second catalytic materials 20, 22 disposed within a zeolite material 12, as previously described in relation to FIGS. 1-3. The powder 48 may be provided within a container 40 having an inlet 42 and an outlet 44, and the powder 48
may be disposed between the inlet 42 and the outlet 44. In this configuration, a gas comprising hydrogen and at least one of carbon monoxide (CO) and carbon dioxide (CO2) may be introduced into the container 40 through the inlet 42. As the gas contacts the powder 48, the powder 48 may catalyze the formation of hydrocarbon molecules having two or more carbon atoms from the carbon monoxide (CO) and carbon dioxide (CO2). In particular, the first catalytic material 20 and the second catalytic material 22 (FIG. 3) may catalyze the formation of methanol from the carbon monoxide (CO) and carbon dioxide (CO2), and the zeolite material 12 may catalyze the formation of hydrocarbon molecules having two or more carbon atoms from the methanol. The hydrocarbon molecules may be collected from the outlet 44 of the container 40 and purified and/or concentrated as necessary or desired.
Referring to FIG. 9, in additional embodiments of the present invention, the catalytic structure 10 may include a plurality of particles, briquettes, or pellets 50, each of which includes first and second catalytic materials 20, 22 disposed within a zeolite material 12, as previously described in relation to FIGS. 1-3. By way of example and not limitation, the pellets 50 may be formed by pressing the powder 48 previously described in relation to FIG. 8 in a die or mold to form the pellets 50. The plurality of pellets 50 may be provided within a container 40, as shown in FIG. 9. In this configuration, a gas comprising at least one of carbon monoxide (CO) and carbon dioxide (CO2) may be introduced into the container 40 through the inlet 42, and the pellets 50 may catalyze the formation of hydrocarbon molecules having two or more carbon atoms from hydrogen and the carbon monoxide (CO) and/or carbon dioxide (CO2), as previously described in relation to FIG. 8.
FIG. 10 is a simplified schematic of a system 60 that embodies teachings of the present invention and that may be used to form hydrocarbon molecules having two or more carbon atoms from carbon monoxide (CO) and/or carbon dioxide (CO2) in the presence of hydrogen using a catalytic structure that embodies teachings of the present invention, such as, for example, the catalytic structure 10 previously described in relation to FIGS. 1-3. By way of example and not limitation, the system 60 may include a reactor 40, a gas-liquid separator 64, and a compressor 66. As previously discussed, the reactor 40 may include a catalytic structure that embodies teachings of the present invention, such as, for example, the catalytic structure 10. The system 60 may further include a first heat exchanger 68A for heating a reactant mixture fed to the reactor 40, and a second heat exchanger 68B for cooling products (and any unreacted reactants and/or reaction byproducts) as they exit the reactor 40.
The system 60 may further include a heating device (not shown) for heating the reactor 40 and the catalytic structure 10 to elevated temperatures. For example, a heating device may be
configured to heat the reactor 40 and the catalytic structure 10 to a temperature between about 2000C and about 5000C. Furthermore, the reactor 40 may be pressurized to between about 0.5 megapascals (5 atmospheres) and about 10 megapascals (100 atmospheres).
As shown in FIG. 10, a reactant mixture 70 that includes hydrogen gas and at least one of carbon monoxide (CO) and carbon dioxide (CO2) may be passed through the first heat exchanger 68A and fed to the reactor 40. As previously discussed, the catalytic structure 10 may catalyze the formation of hydrocarbon molecules having two or more carbon atoms from the hydrogen and carbon monoxide (CO) and/or carbon dioxide (CO2). A product mixture 72 (which may include such hydrocarbon molecules), together with any unreacted reactant gasses 74 and reaction byproducts, may be collected from the reactor 40 and passed through the second heat exchanger 68B to the gas-liquid separator 64. The gas liquid separator 64 may be used to separate liquid hydrocarbon products of the product mixture 72 from the unreacted reactant gases 74. The unreacted reactant gasses 74 may be re-pressurized as necessary using the compressor 66 and recombined with the reactant mixture 70 through the three-way valve 78, as shown in FIG. 10.
The liquid hydrocarbon products in the product mixture 72 collected from the gas-liquid separator 64 may then be further processed as necessary or desired. For example, additional distillation equipment (not shown) may be used to purify and concentrate the various hydrocarbon components in the product mixture 72 as necessary or desired. The catalytic structures, systems, and methods described herein may be used to catalyze the conversion of hydrogen and at least one of carbon monoxide and carbon dioxide to hydrocarbons having two or more carbon atoms with improved catalytic activity and selectivity relative to known catalytic structures, systems, and methods. Furthermore, the catalytic structures, systems, and methods described herein may facilitate economic utilization of carbon dioxide from stationary carbon dioxide sources, such as coal-powered and hydrocarbon-powered electricity generation plants, which otherwise may be vented to atmosphere. Furthermore, the methods described herein may be used to fabricate various catalytic structures, other than those described herein, that include a bi-modal (microporous and mesorporous) or multi-modal (microporous, mesoporous, and macroporous) zeolite material and a metal and/or metal oxide catalyst material disposed on and/or in the zeolite material. Such catalytic structures may be bi- functional. In other words, the zeolite material itself may function as one catalytic material, while the catalytic material disposed on and/or in the zeolite material may function as a second catalytic material. In addition to the synthesis of hydrocarbon molecules from hydrogen and carbon monoxide and/or carbon dioxide, such bi-functional catalytic structures may be useful in
many additional applications where it is necessary or desirable to provide different catalytic functions to a single catalytic structure or material.
While the invention may be susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, it should be understood that the invention is not intended to be limited to the particular forms disclosed. Rather, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the following appended claims.
Claims
1. A catalytic structure comprising: a substantially crystalline zeolite material; a first plurality of pores substantially defined by a crystal structure of the substantially crystalline zeolite material; a second plurality of pores dispersed throughout the substantially crystalline zeolite material; a metallic material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores; and a metal oxide material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.
2. The catalytic structure of claim 1, wherein the metallic material comprises a plurality of metallic particles.
3. The catalytic structure of claim 2, wherein the plurality of metallic particles has an average particle size of less than about 500 angstroms.
4. The catalytic structure of claim 1, wherein the metallic material comprises at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.
5. The catalytic structure of claim 1, wherein the metal oxide material comprises a plurality of metal oxide particles.
6. The catalytic structure of claim 1, wherein the plurality of metal oxide particles has an average particle size of less than about 500 angstroms.
7. The catalytic structure of claim 1, wherein the metal oxide material comprises at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.
8. The catalytic structure of claim 1, wherein the metal material comprise copper and the metal oxide material comprises zinc oxide.
9. The catalytic structure of claim 1, wherein the second plurality of pores comprises a plurality of elongated channels.
10. The catalytic structure of claim 9, wherein each elongated channel of the plurality of elongated channels is generally cylindrical and has an average diameter in a range extending from about 20 angstroms to about 500 angstroms.
11. The catalytic structure of claim 9, wherein the second plurality of pores further comprises a plurality of generally spherical pores.
12. The catalytic structure of claim 1, wherein the zeolite material has a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.
13. The catalytic structure of claim 12, wherein the zeolite material comprises an aluminosilicate-based material, an aluminophosphate-based material, or a silicoaluminophosphate-based material.
14. The catalytic structure of claim 13, wherein the zeolite material comprises ZSM-
5.
15. The catalytic structure of claim 1, wherein the first plurality of pores comprises a plurality of micropores and the second plurality of pores comprises a plurality of mesopores.
16. A catalytic structure comprising: a zeolite material capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, the zeolite material comprising: a first plurality of pores substantially defined by a crystal structure of the zeolite material; and a second plurality of pores dispersed throughout the zeolite material; at least one catalytic material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores, the at least one catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen.
17. The catalytic structure of claim 16, wherein the at least one catalytic material comprises a plurality of metallic particles.
18. The catalytic structure of claim 17, wherein the plurality of metallic particles has an average particle size of less than about 500 angstroms.
19. The catalytic structure of claim 17, wherein each metallic particle of the plurality of metallic particles comprises at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.
20. The catalytic structure of claim 17, wherein the at least one catalytic material further comprises a plurality of metal oxide particles.
21. The catalytic structure of claim 20, wherein the plurality of metal oxide particles has an average particle size of less than about 500 angstroms.
22. The catalytic structure of claim 20, wherein each metal oxide particle comprises at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.
23. The catalytic structure of claim 16, wherein the at least one catalytic material comprises copper and zinc oxide.
24. The catalytic structure of claim 16, wherein the second plurality of pores comprises a plurality of elongated channels.
25. The catalytic structure of claim 24, wherein each elongated channel of the plurality of elongated channels is generally cylindrical and has an average diameter in a range extending from about 20 angstroms to about 500 angstroms.
26. The catalytic structure of claim 24, wherein the second plurality of pores further comprises a plurality of generally spherical pores.
27. The catalytic structure of claim 16, wherein the zeolite material has a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.
28. The catalytic structure of claim 27, wherein the zeolite material comprises an aluminosilicate-based material, an aluminophosphate -based material, or a silicoaluminophosphate-based material.
29. The catalytic structure of claim 28, wherein the zeolite material comprises ZSM-
5.
30. The catalytic structure of claim 16, wherein the first plurality of pores comprises a plurality of micropores and the second plurality of pores comprises a plurality of mesopores.
31. A method of fabricating a catalytic structure, the method comprising: forming a zeolite material at least partially around at least one template structure, the zeolite material capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol; removing the at least one template structure from within the zeolite material; introducing at least one catalytic material into the zeolite material, the at least one catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen.
32. The method of claim 31 , wherein introducing at least one catalytic material into the zeolite material comprises introducing a plurality of metallic particles into the zeolite material.
33. The method of claim 32, wherein introducing a plurality of metallic particles into the zeolite material comprises introducing a plurality of metallic particles having an average particle size of less than about 500 angstroms into the zeolite material.
34. The method of claim 32, further comprising selecting each metallic particle of the plurality of metallic particles to comprise at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.
35. The method of claim 32, wherein introducing at least one catalytic material into the zeolite material further comprises introducing a plurality of metal oxide particles into the zeolite material.
36. The method of claim 35, wherein introducing a plurality of metal oxide particles into the zeolite material comprises introducing a plurality of metal oxide particles having an average particle size of less than about 200 angstroms into the zeolite material.
37. The method of claim 35, further comprising selecting each metal oxide particle of the plurality of metal oxide particles to comprise at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.
38. The method of claim 31 , wherein introducing at least one catalytic material into the zeolite material comprises introducing copper and zinc oxide into the zeolite material.
39. The method of claim 38, wherein introducing copper into the zeolite material and introducing zinc oxide into the zeolite material each comprise introducing a nitrate solution into the zeolite material and heating the zeolite material in air to temperatures of greater than about 1000C.
40. The method of claim 31 , wherein forming a zeolite material at least partially around at least one template structure comprises forming a zeolite material around a plurality of elongated template structures, and wherein removing the at least one template structure from within the zeolite material comprises forming a plurality of elongated channels in the zeolite material.
41. The method of claim 40, wherein forming a plurality of elongated channels comprises forming a plurality of generally cylindrical channels having an average diameter in a range extending from about 20 angstroms to about 500 angstroms in the zeolite material.
42. The method of claim 40, wherein forming a zeolite material at least partially around at least one template structure further comprises forming a zeolite material around a plurality of generally spherical template structures, and wherein removing the at least one
template structure from within the zeolite material comprises forming a plurality of generally spherical pores in the zeolite material.
43. The method of claim 31 , wherein forming a zeolite material comprises forming a zeolite material having a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.
44. The method of claim 43, wherein forming a zeolite material comprises forming an aluminosilicate-based material, an aluminophosphate-based material, or a silicoaluminophosphate-based material.
45. The method of claim 44, wherein forming a zeolite material comprises forming ZSM-5.
46. The method of claim 31 , wherein forming a zeolite material at least partially around at least one template structure comprises forming a zeolite material at least partially around at least one template structure comprising at least one of a plurality of carbon nanoparticles and a plurality of carbon nano wires.
47. The method of claim 31 , wherein forming a zeolite material at least partially around at least one template structure comprises forming a zeolite material at least partially around each of a plurality of carbon nanotubes.
48. The method of claim 47, wherein introducing a first catalytic material comprises impregnating at least one carbon nanotube of the plurality of carbon nanotubes with a solution comprising at least one element of at least one of the first catalytic material and the second catalytic material.
49. A method of synthesizing hydrocarbon molecules having two or more carbon atoms, the method comprising: contacting hydrogen and at least one of carbon monoxide and carbon dioxide with a catalytic structure at a temperature greater than about 2000C and a pressure greater than about 0.5 megapascals, the catalytic structure comprising:
a zeolite material capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, the zeolite material comprising: a first plurality of pores substantially defined by interstitial spaces within a crystal structure of the zeolite material; and a second plurality of pores dispersed throughout the zeolite material; and at least one catalytic material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores, the first catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen.
50. The method of claim 49, wherein contacting at least one of carbon monoxide and carbon dioxide with a catalytic structure comprises supplying a mixture of hydrogen and at least one of carbon monoxide and carbon dioxide to a reactor containing the catalytic structure.
51. The method of claim 49, further comprising: removing reaction products and unreacted reactants from the reactor; cooling the reaction products and unreacted reactants; and separating unreacted reactants from the reaction products, the reaction products comprising hydrocarbon molecules having two or more carbon atoms.
52. The method of claim 51 , further comprising recombining the separated unreacted reactants with the mixture supplied to the reactor.
53. The method of claim 49, wherein the catalytic structure comprises a plurality of pellets each comprising the zeolite material and the at least one catalytic material.
54. The method of claim 49, wherein the at least one catalytic material comprises a plurality of metallic particles.
55. The method of claim 54, wherein the plurality of metallic particles has an average particle size of less than about 500 angstroms.
56. The method of claim 54, further comprising selecting each metallic particle of the plurality of metallic particles to comprise at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.
57. The method of claim 54, wherein the at least one catalytic material further comprises a plurality of metal oxide particles.
58. The method of claim 57, wherein the plurality of metal oxide particles has an average particle size of less than about 500 angstroms.
59. The method of claim 57 further comprising selecting each metal oxide particle to comprise at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.
60. The method of claim 49, wherein the at least one catalytic material comprises copper and zinc oxide.
61. The method of claim 49, wherein the second plurality of pores comprises a plurality of elongated channels.
62. The method of claim 61, wherein each elongated channel of the plurality of elongated channels is generally cylindrical and has an average diameter in a range extending from about 20 angstroms to about 500 angstroms.
63. The method of claim 61, wherein the second plurality of pores further comprises a plurality of generally spherical pores.
64. The method of claim 49, wherein the zeolite material has a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.
65. The method of claim 64, wherein the zeolite material comprises an aluminosilicate-based material, an aluminophosphate -based material, or a silicoaluminophosphate-based material.
66. The method of claim 65, wherein the zeolite material comprises ZSM-5.
67. The method of claim 49, wherein the first plurality of pores comprises a plurality of micropores and the second plurality of pores comprises a plurality of mesopores.
68. A system for synthesizing hydrocarbon molecules having two or more carbon atoms from hydrogen and at least one of carbon monoxide and carbon dioxide, the system comprising: a reactor configured to receive a reactant mixture comprising hydrogen and at least one of carbon monoxide and carbon dioxide; and a catalytic structure disposed within the reactor, the catalytic structure comprising: a zeolite material capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, the zeolite material comprising: a first plurality of pores substantially defined by a crystal structure of the zeolite material; and a second plurality of pores dispersed throughout the zeolite material; and at least one catalytic material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores, the first catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen.
69. The system of claim 68, further comprising a device configured to heat the catalytic structure to a temperature of greater than about 2000C.
70. The system of claim 69, further comprising a device configured to pressurize the reactor to a pressure of greater than about 0.5 megapascals.
71. The system of claim 68, wherein the at least one catalytic material comprises a plurality of metallic particles.
72. The system of claim 71, wherein the plurality of metallic particles has an average particle size of less than about 500 angstroms.
73. The system of claim 71 , wherein each metallic particle of the plurality of metallic particles comprises at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.
74. The system of claim 71, wherein the at least one catalytic material further comprises a plurality of metal oxide particles.
75. The system of claim 74, wherein the plurality of metal oxide particles has an average particle size of less than about 200 angstroms.
76. The system of claim 74, wherein each metal oxide particle comprises at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.
77. The system of claim 68, wherein the at least one catalytic material comprises copper and zinc oxide.
78. The system of claim 68, wherein the second plurality of pores comprises a plurality of elongated channels.
79. The system of claim 78, wherein each elongated channel of the plurality of elongated channels is generally cylindrical and has an average diameter in a range extending from about 20 angstroms to about 500 angstroms.
80. The system of claim 78, wherein the second plurality of pores further comprises a plurality of generally spherical pores.
81. The system of claim 68, wherein the zeolite material has a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.
82. The system of claim 81, wherein the zeolite material comprises an aluminosilicate-based material, an aluminophosphate -based material, or a silicoaluminophosphate-based material.
83. The system of claim 82, wherein the zeolite material comprises ZSM-5.
84. The system of claim 68, wherein the first plurality of pores comprises a plurality pores and the second plurality of pores comprises a plurality of mesopores.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/464,566 | 2006-08-15 | ||
| US11/464,566 US7879749B2 (en) | 2006-08-15 | 2006-08-15 | Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2008021602A2 true WO2008021602A2 (en) | 2008-02-21 |
| WO2008021602A3 WO2008021602A3 (en) | 2008-05-02 |
Family
ID=39082831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2007/069005 WO2008021602A2 (en) | 2006-08-15 | 2007-05-16 | Structures including catalytic materials disposed within porous zeolite materials, systems and methods for using the same, and methods of fabricating catalytic structures |
Country Status (2)
| Country | Link |
|---|---|
| US (3) | US7879749B2 (en) |
| WO (1) | WO2008021602A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125049A1 (en) * | 2010-04-08 | 2011-10-13 | Basf Se | Cu-cha/fe-mfi mixed zeolite catalyst and process for treating nox in gas streams using the same |
| US8480964B2 (en) | 2011-07-05 | 2013-07-09 | King Fahd University Of Petroleum And Minerals | Plate reactor |
| US9352307B2 (en) | 2010-04-08 | 2016-05-31 | Basf Corporation | Cu-CHA/Fe-MFI mixed zeolite catalyst and process for the treatment of NOx in gas streams |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7879749B2 (en) * | 2006-08-15 | 2011-02-01 | Battelle Energy Alliance, Llc | Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons |
| KR101504776B1 (en) * | 2007-07-19 | 2015-03-20 | 도다 고교 가부시끼가이샤 | Catalyst for decomposing hydrocarbon, process for producing a mixed reformed gas and fuel cell system using the catalyst |
| US9404045B2 (en) | 2011-02-17 | 2016-08-02 | AMG Chemistry and Catalysis Consulting, LLC | Alloyed zeolite catalyst component, method for making and catalytic application thereof |
| US10987661B2 (en) | 2011-02-17 | 2021-04-27 | AMG Chemistry and Catalysis Consulting, LLC | Alloyed zeolite catalyst component, method for making and catalytic application thereof |
| CN103752323B (en) * | 2014-01-02 | 2016-04-27 | 上海大学 | There is the preparation method of the denitrating catalyst of nanometer many squashes shape spinel structure |
| WO2016116611A1 (en) | 2015-01-22 | 2016-07-28 | Haldor Topsøe A/S | Hydrogen rejection in methanol to hydrocarbon process |
| US10695756B2 (en) * | 2015-06-12 | 2020-06-30 | Enerkem, Inc. | Metal-loaded zeolite catalysts for the halogen-free conversion of dimethyl ether to methyl acetate |
| ITUB20154976A1 (en) * | 2015-10-16 | 2017-04-16 | Lavazza Luigi Spa | Process for the treatment of gaseous effluents developed in a coffee roasting plant. |
| US20190046964A1 (en) * | 2016-03-16 | 2019-02-14 | Sabic Global Technologies B.V. | Synthesis of sapo-34 and use in chloromethane to olefins reactions |
| JP7316934B2 (en) | 2017-05-31 | 2023-07-28 | 古河電気工業株式会社 | Hydrodesulfurization catalyst structure, hydrodesulfurization apparatus equipped with the catalyst structure, and method for producing hydrodesulfurization catalyst structure |
| WO2018221696A1 (en) | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | Oxidation catalyst structure for exhaust gas purification and production method thereof, exhaust gas treatment device for vehicle, catalyst molded body, and gas purification method |
| JP7269169B2 (en) | 2017-05-31 | 2023-05-08 | 古河電気工業株式会社 | Methanol reforming catalyst structure, apparatus for methanol reforming, method for producing methanol reforming catalyst structure, and method for producing at least one of olefins and aromatic hydrocarbons |
| CN110678258A (en) | 2017-05-31 | 2020-01-10 | 国立大学法人北海道大学 | Functional structure and method for manufacturing functional structure |
| CN110730687A (en) | 2017-05-31 | 2020-01-24 | 古河电气工业株式会社 | Catalyst structure for catalytic cracking or hydrodesulfurization, catalytic cracking device and hydrodesulfurization device each having the catalyst structure, and method for producing catalyst structure for catalytic cracking or hydrodesulfurization |
| CN110678259A (en) | 2017-05-31 | 2020-01-10 | 国立大学法人北海道大学 | Functional structure and method for manufacturing functional structure |
| WO2018221693A1 (en) | 2017-05-31 | 2018-12-06 | 国立大学法人北海道大学 | Functional structure and production method for functional structure |
| CN110691645A (en) | 2017-05-31 | 2020-01-14 | 国立大学法人北海道大学 | Functional structure and method for manufacturing functional structure |
| US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
| JP7306990B2 (en) | 2017-05-31 | 2023-07-11 | 古河電気工業株式会社 | CO-shift or reverse-shift catalyst structures and methods for making same, CO-shift or reverse-shift reactors, methods for producing carbon dioxide and hydrogen, and methods for producing carbon monoxide and water |
| CN107500246B (en) * | 2017-08-30 | 2019-06-04 | 北京三聚环保新材料股份有限公司 | A kind of catalyst microspheres profiled part and its application |
| WO2024007201A1 (en) * | 2022-07-06 | 2024-01-11 | 苏州大学 | Copper-doped zinc oxide nanorod, preparation method therefor, and use thereof in piezoelectric-photocatalytic removal of organic pollutants |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5043307A (en) * | 1986-01-03 | 1991-08-27 | Mobil Oil Corp. | Modified crystalline aluminosilicate zeolite catalyst and its use in the production of lubes of high viscosity index |
| US5348924A (en) * | 1989-09-29 | 1994-09-20 | Exxon Research & Engineering Co. | Zeolite aggregates and catalysts |
| US5786294A (en) * | 1996-05-10 | 1998-07-28 | Northwestern University | Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure |
| US6982287B2 (en) * | 1999-08-17 | 2006-01-03 | Battelle Memorial Institute | Catalyst structure and method of fischer-tropsch synthesis |
Family Cites Families (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3615217A (en) * | 1966-06-27 | 1971-10-26 | Catalysts & Chemicals Inc | Low temperature copper-zinc shift reaction catalysts and methods for their preparation |
| US3907715A (en) * | 1968-09-14 | 1975-09-23 | Chiyoda Chem Eng Construct Co | Process for producing metal containing composition |
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| US4302619A (en) * | 1980-06-04 | 1981-11-24 | Mobil Oil Corporation | Control of CO emissions in a process for producing gasoline from methanol |
| DE3381679D1 (en) * | 1982-12-13 | 1990-07-26 | Ici Plc | METHANOL SYNTHESIS AND THE REQUIRED CATALYST. |
| US4556821A (en) * | 1984-03-15 | 1985-12-03 | Rca Corporation | Color image display system having an improved external magnetic shield |
| GB8714539D0 (en) * | 1987-06-22 | 1987-07-29 | Ici Plc | Catalysts |
| EP0987220A1 (en) * | 1998-09-17 | 2000-03-22 | Technische Universiteit Delft | Mesoporous amorphous silicate materials and process for the preparation thereof |
| US5378440A (en) * | 1990-01-25 | 1995-01-03 | Mobil Oil Corp. | Method for separation of substances |
| US5344849A (en) * | 1990-10-31 | 1994-09-06 | Canada Chemical Corporation | Catalytic process for the production of hydrocarbons |
| US5348643A (en) * | 1991-03-12 | 1994-09-20 | Mobil Oil Corp. | Catalytic conversion with improved catalyst |
| US5456821A (en) | 1991-03-12 | 1995-10-10 | Mobil Oil Corp. | Catalytic conversion with improved catalyst |
| US5366948A (en) * | 1991-03-12 | 1994-11-22 | Mobil Oil Corp. | Catalyst and catalytic conversion therewith |
| US5506273A (en) * | 1991-12-06 | 1996-04-09 | Agency Of Industrial Science And Technology | Catalyst for hydrogenation and method for hydrogenation therewith |
| US5466646A (en) * | 1992-08-18 | 1995-11-14 | Worcester Polytechnic Institute | Process for the preparation of solid state materials and said materials |
| US5362697A (en) * | 1993-04-26 | 1994-11-08 | Mobil Oil Corp. | Synthetic layered MCM-56, its synthesis and use |
| US5689024A (en) * | 1994-06-03 | 1997-11-18 | Mobil Oil Corporation | Use of crystalline SUZ-9 |
| FR2727397B1 (en) * | 1994-11-30 | 1997-01-24 | Inst Francais Du Petrole | PROCESS FOR THE SYNTHESIS OF ZEOLITHS AND MESOPOROUS SOLIDS FROM A HOMOGENEOUS SOLUTION IN A SEMI-OPEN SYSTEM |
| US5493064A (en) * | 1994-12-13 | 1996-02-20 | Exxon Research And Engineering Company | Noble metal large pore zeolyte catalyst for methanol-ethanol coupling |
| DE19506843A1 (en) * | 1995-02-28 | 1996-08-29 | Studiengesellschaft Kohle Mbh | Microporous amorphous mixed metal oxides for shape-selective catalysis |
| DE19545042A1 (en) * | 1995-12-02 | 1997-06-05 | Studiengesellschaft Kohle Mbh | Amorphous microporous mixed oxide catalysts with controlled surface polarity for selective heterogeneous catalysis adsorption and material separation |
| US5919430A (en) * | 1996-06-19 | 1999-07-06 | Degussa Aktiengesellschaft | Preparation of crystalline microporous and mesoporous metal silicates, products produced thereby and use thereof |
| US5680278A (en) * | 1996-08-08 | 1997-10-21 | Quantum Corporation | Apparatus for combining linear and rotational motion of an azimuth read/write head |
| JP3341278B2 (en) * | 1997-03-31 | 2002-11-05 | 株式会社豊田中央研究所 | Mesopore material and method for producing the same |
| US6612373B2 (en) * | 1998-10-06 | 2003-09-02 | Richard P. Brennan | Apparatus and method for off-road vehicle fire protection and fire suppression |
| US6403743B1 (en) * | 1999-09-14 | 2002-06-11 | Exxonmobil Chemical Patents Inc. | Petroleum resins and their production with supported catalyst |
| US6620402B2 (en) * | 1999-12-06 | 2003-09-16 | Haldor Topsoe A.S | Method of preparing zeolite single crystals with straight mesopores |
| US6398946B1 (en) * | 1999-12-22 | 2002-06-04 | Chevron U.S.A., Inc. | Process for making a lube base stock from a lower molecular weight feedstock |
| US6497812B1 (en) * | 1999-12-22 | 2002-12-24 | Chevron U.S.A. Inc. | Conversion of C1-C3 alkanes and fischer-tropsch products to normal alpha olefins and other liquid hydrocarbons |
| US7048781B1 (en) * | 2002-10-07 | 2006-05-23 | Ada Technologies, Inc. | Chemically-impregnated silicate agents for mercury control |
| US6627572B1 (en) * | 2002-03-22 | 2003-09-30 | Sud-Chemie Inc. | Water gas shift catalyst |
| US6693057B1 (en) * | 2002-03-22 | 2004-02-17 | Sud-Chemie Inc. | Water gas shift catalyst |
| US6759360B2 (en) * | 2002-03-29 | 2004-07-06 | Exxonmobil Chemical Patent Inc. | Interior surface modifications of molecular sieves with organometallic reagents and the use thereof for the conversion of oxygenates to olefins |
| US6638892B1 (en) * | 2002-04-18 | 2003-10-28 | Conocophillips Company | Syngas conversion and catalyst system employed therefor |
| US6620983B1 (en) * | 2002-06-12 | 2003-09-16 | Exxonmobil Chemical Patents Inc. | Synthesis of aluminophosphates and silicoaluminophosphates |
| US6680278B2 (en) | 2002-06-12 | 2004-01-20 | Exxonmobil Chemical Patents, Inc. | Synthesis of silicoaluminophosphates |
| US7005118B2 (en) * | 2002-07-25 | 2006-02-28 | Instituto Mexicano Del Petroleo | Synthetic mesoporous material with radially assembled nanotubes |
| US20040064008A1 (en) * | 2002-09-30 | 2004-04-01 | Torsten Maurer | Molecular sieve catalyst composition |
| US6812373B2 (en) * | 2002-12-12 | 2004-11-02 | Exxonmobil Chemical Patents Inc. | Modified metalloaluminophosphate molecular sieves |
| US6906233B2 (en) * | 2002-12-12 | 2005-06-14 | Exxon Mobil Chemical Patents Inc. | Modified metalloaluminophosphate molecular sieves |
| US7022888B2 (en) * | 2003-03-27 | 2006-04-04 | Council Of Scientific And Industrial Research | Process for the simultaneous conversion of methane and organic oxygenate to C2 to C10 hydrocarbons |
| US7172813B2 (en) * | 2003-05-20 | 2007-02-06 | Burgener Ii Robert H | Zinc oxide crystal growth substrate |
| US7589041B2 (en) * | 2004-04-23 | 2009-09-15 | Massachusetts Institute Of Technology | Mesostructured zeolitic materials, and methods of making and using the same |
| US7514575B2 (en) * | 2005-05-06 | 2009-04-07 | Battelle Energy Allicance, Llc | Production of biodiesel using expanded gas solvents |
| US7879749B2 (en) * | 2006-08-15 | 2011-02-01 | Battelle Energy Alliance, Llc | Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons |
| US7592291B2 (en) * | 2006-08-15 | 2009-09-22 | Batelle Energy Alliance, Llc | Method of fabricating a catalytic structure |
-
2006
- 2006-08-15 US US11/464,566 patent/US7879749B2/en not_active Expired - Fee Related
-
2007
- 2007-05-16 WO PCT/US2007/069005 patent/WO2008021602A2/en active Application Filing
-
2010
- 2010-12-16 US US12/970,689 patent/US8226909B2/en not_active Expired - Fee Related
- 2010-12-16 US US12/970,643 patent/US20110092356A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5043307A (en) * | 1986-01-03 | 1991-08-27 | Mobil Oil Corp. | Modified crystalline aluminosilicate zeolite catalyst and its use in the production of lubes of high viscosity index |
| US5348924A (en) * | 1989-09-29 | 1994-09-20 | Exxon Research & Engineering Co. | Zeolite aggregates and catalysts |
| US5786294A (en) * | 1996-05-10 | 1998-07-28 | Northwestern University | Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure |
| US6982287B2 (en) * | 1999-08-17 | 2006-01-03 | Battelle Memorial Institute | Catalyst structure and method of fischer-tropsch synthesis |
Non-Patent Citations (4)
| Title |
|---|
| AGNY ET AL.: 'Synthesis of Methanol from Carbon Monoxide and Hydrogen Over a Copper-ZincOxide-Alumina Catalyst' IND. ENG. CHEM. PROD. RES. DEV. vol. 24, 1985, pages 50 - 55 * |
| GOVIND ET AL.: 'Zeolite-Catalyzed Hydrocarbon Formation From Methanol: Density Functional Simulations' INT. J. MOL. SCI. vol. 3, 2002, pages 423 - 434 * |
| KRESGE ET AL.: 'Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-Crystal Template Mechanism' NATURE vol. 359, 1992, pages 710 - 712 * |
| TANG ET AL.: 'Mono-sized Single-walled Carbon Nanotubes Formed in Channels of ALP4-5 Single Crystal' APPLIED PHYSICS LETTERS vol. 73, 19 October 1998, pages 2287 - 2289 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125049A1 (en) * | 2010-04-08 | 2011-10-13 | Basf Se | Cu-cha/fe-mfi mixed zeolite catalyst and process for treating nox in gas streams using the same |
| US9352307B2 (en) | 2010-04-08 | 2016-05-31 | Basf Corporation | Cu-CHA/Fe-MFI mixed zeolite catalyst and process for the treatment of NOx in gas streams |
| US8480964B2 (en) | 2011-07-05 | 2013-07-09 | King Fahd University Of Petroleum And Minerals | Plate reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| US8226909B2 (en) | 2012-07-24 |
| US20110085944A1 (en) | 2011-04-14 |
| US7879749B2 (en) | 2011-02-01 |
| US20080045403A1 (en) | 2008-02-21 |
| US20110092356A1 (en) | 2011-04-21 |
| WO2008021602A3 (en) | 2008-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7879749B2 (en) | Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons | |
| US7592291B2 (en) | Method of fabricating a catalytic structure | |
| Wang et al. | Direct conversion of CO2 to aromatics with high yield via a modified Fischer-Tropsch synthesis pathway | |
| Wei et al. | Towards the development of the emerging process of CO 2 heterogenous hydrogenation into high-value unsaturated heavy hydrocarbons | |
| Li et al. | Hydrogenation of CO2 to dimethyl ether over tandem catalysts based on biotemplated hierarchical ZSM-5 and Pd/ZnO | |
| Bawah et al. | Syngas production from CO2 reforming of methane over Ni supported on hierarchical silicalite-1 fabricated by microwave-assisted hydrothermal synthesis | |
| WO2016038020A2 (en) | Catalytic materials based on functionalized zsm-5 | |
| Saenluang et al. | Hierarchical nanospherical ZSM-5 nanosheets with uniform Al distribution for alkylation of benzene with ethanol | |
| Li et al. | Design and Synthesis of Bioinspired ZnZrO x &Bio-ZSM-5 Integrated Nanocatalysts to Boost CO2 Hydrogenation to Light Olefins | |
| US20110201860A1 (en) | Process for conversion of alkanes to aromatics | |
| Rimaz et al. | A comprehensive review on sustainability-motivated applications of SAPO-34 molecular sieve | |
| CN113498360A (en) | Catalyst for producing light olefins from C4-C7 hydrocarbons | |
| US20190001311A1 (en) | Zeolitic 3d scaffolds with tailored surface topography for methanol conversion with light olefins selectivity | |
| Hua et al. | Direct hydrogenation of carbon dioxide to value-added aromatics | |
| Li et al. | Assembly of ZnZrOx and ZSM-5 on hierarchically porous bio-derived SiO2 platform as bifunctional catalysts for CO2 hydrogenation to aromatics | |
| Magzoub et al. | Directly printed oxide/ZSM-5 bifunctional catalysts for methanol conversion to dimethyl ether with exceptional stability, conversion, and selectivity | |
| US11161093B1 (en) | Gold-decorated magnesium silicate catalyst for producing light olefins | |
| CN112469666A (en) | Method for continuous synthesis of zeolitic materials using seeds loaded with organic template | |
| Son et al. | Preparation and modification of zeolite A from kaolin for catalytic methanation of carbon dioxide | |
| Meng et al. | Tailoring the pore size of zeolite Y as the support of diesel aromatic saturation catalyst | |
| Firouzjaee et al. | Synthesis procedure and industrial applications of NaY zeolite for various processes: a review | |
| Leung et al. | Metal-loaded zeolites in ammonia decomposition catalysis | |
| Khaledi et al. | Influence of surface design on performance of MnO‐decorated nanocatalyst for olefin production from methanol: ZSM‐5@ MnO core–shell versus MnO/ZSM‐5 dispersed nanocatalysts | |
| Anbia et al. | Synthesis and characterization of a novel modified ANA zeolite membrane | |
| Xiang et al. | Facile synthesis of hierarchical SAPO-56 zeolite as a highly efficient catalyst for CO2 hydrogenation to methanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07840182 Country of ref document: EP Kind code of ref document: A2 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| NENP | Non-entry into the national phase |
Ref country code: RU |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 07840182 Country of ref document: EP Kind code of ref document: A2 |